U.S. patent application number 16/468372 was filed with the patent office on 2019-10-31 for quantum dot film and applications thereof.
The applicant listed for this patent is SABIC GLOBAL TECHNOLOGIES B.V.. Invention is credited to Soonyoung HYUN, Chunim LEE, Jong Woo LEE, Seongnam LEE, Sunyoung LEE, Jeongmin LIM, Mohamed Shaker MOHAMED, Kahee SHIN.
Application Number | 20190334107 16/468372 |
Document ID | / |
Family ID | 60943059 |
Filed Date | 2019-10-31 |
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United States Patent
Application |
20190334107 |
Kind Code |
A1 |
LEE; Sunyoung ; et
al. |
October 31, 2019 |
QUANTUM DOT FILM AND APPLICATIONS THEREOF
Abstract
A film for light emitting devices, the film formed from a
process including a quantum dot solution disposed between a first
layer and a second layer, where at least one of the first layer and
second layer is a protective layer, and where the protective layer
is formed by mixing a barrier polymer with a scavenger.
Inventors: |
LEE; Sunyoung; (Seoul,
KR) ; LEE; Chunim; (Gyeonggi-do, KR) ;
MOHAMED; Mohamed Shaker; (Gyeonggi-do, KR) ; LEE;
Seongnam; (Seoul, KR) ; LIM; Jeongmin;
(Gyeonggi-do, KR) ; SHIN; Kahee; (Seoul, KR)
; LEE; Jong Woo; (Seoul, KR) ; HYUN;
Soonyoung; (Gyeonggi-do, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC GLOBAL TECHNOLOGIES B.V. |
Bergen op Zoom |
|
NL |
|
|
Family ID: |
60943059 |
Appl. No.: |
16/468372 |
Filed: |
December 12, 2017 |
PCT Filed: |
December 12, 2017 |
PCT NO: |
PCT/IB2017/057855 |
371 Date: |
June 11, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62433408 |
Dec 13, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 51/0007 20130101;
H01L 51/5256 20130101; H01L 33/06 20130101; H01L 51/502 20130101;
H01L 51/5253 20130101; B82Y 20/00 20130101; H01L 51/5259
20130101 |
International
Class: |
H01L 51/50 20060101
H01L051/50; H01L 51/00 20060101 H01L051/00; H01L 51/52 20060101
H01L051/52; H01L 33/06 20060101 H01L033/06 |
Claims
1. A light emitting film comprising: a first layer and a second
layer; a quantum dot layer disposed between the first layer and the
second layer; and wherein at least one of the first layer and the
second layer is a protective layer, the protective layer comprising
a barrier polymer and a scavenger, wherein the protective layer
inhibits permeation of at least oxygen and moisture into the
quantum dot layer.
2. The film of claim 1, wherein the scavenger is a phenolic
acid.
3. The film of claim 1, wherein the scavenger is selected from the
group consisting of galic acid, p-coumaric acid, caffeic acid,
rosemaric acid and protocatechuic acid.
4. The film of claim 1, wherein the first layer is a barrier layer
and wherein the quantum dot layer is disposed on the barrier layer
using a solution coating process.
5. The film of claim 1, wherein the first layer is a protective
layer and the second layer is a protective layer, wherein the first
layer a substrate underlying the barrier polymer and the
scavenger.
6. The film of claim 1, wherein the protective layer comprises an
inorganic layer and the inorganic layer comprises a
polysilazane-based polymer, a polysiloxane-based polymer, or a
combination thereof.
7. The film of claim 1, wherein the protective layer comprises a
hybrid layer and the hybrid layer comprises an organic component
and inorganic component.
8. The film of claim 1, further comprising a functional layer
provided outward of the protective layer.
9. The film of claim 1, wherein the functional layer is a
diffuser.
10. The film of claim 1, wherein the functional layer is a
prism.
11. The film of claim 1, wherein the second layer is disposed on
the quantum dot layer using a solution coating process.
12. The film of claim 1, wherein the scavenger is present in an
amount less than 0.5 wt. %.
13. The film of claim 1, wherein the scavenger is present in an
amount from about 0.01% to about 0.5%.
14. The film of claim 1, wherein the protecting layer has a
thickness in the range of about 50 nanometers to about 50
micrometers.
15. A light emitting device comprising the film of claim 1.
16. A film for light emitting devices, the film formed from a
process comprising: disposing a quantum dot solution between a
first layer and a second layer to form a quantum dot layer, where
at least one of the first layer and second layer is a protective
layer; and wherein the protective layer is formed by mixing a
barrier polymer with a scavenger.
17. The film of claim 16, wherein the barrier polymer comprises a
polysilazane-based polymer, a polysiloxane-based polymer, or a
combination thereof.
18. The film of claim 16, wherein the protective layer further
comprises a functional layer.
19. A light emitting device comprising the film of claim 16.
20. A method comprising: disposing a quantum dot solution on a
first layer; applying a second layer to the quantum dot solution;
wherein at least one of the first layer and second layer are a
protective layer formed by providing a barrier polymer with a
scavenger, wherein the scavenger absorbs at least one of oxygen and
water to inhibit the at least one of oxygen and water from reacting
with the quantum dot solution; and curing the first layer, second
layer and quantum dot solution to form a film comprising a stack of
the first layer, the quantum dot layer, and the second layer.
Description
TECHNICAL FIELD
[0001] The disclosure generally relates to light emitting device
and methods and more particularly to methods and structures
utilizing a quantum dot film.
BACKGROUND
[0002] Direct conversion of electricity into light using
semiconductor-based light-emitting diodes (LEDs) is widely accepted
one of the most promising approaches to more efficient lighting.
LEDs demonstrate high brightness, long operational lifetime, and
low energy consumption performance that far surpass that of
conventional lighting systems such as incandescent and fluorescent
light sources. The LED field is currently dominated by
semiconductor quantum-well emitters (based, e.g., on
indium-gallium-nitride (InGaN)/gallium nitride (GaN)) fabricated by
epitaxial methods on crystalline substrates (e.g., sapphire). These
structures are highly efficient, reliable, mature and bright, but
structural defects at the substrate and semiconductor interface
caused by lattice mismatch and heating during operation generally
limits such devices to point light source with limited flexible
compatibility.
[0003] OLEDs are easily amendable to low-temperature, large-area
processing, including fabrication on flexible substrates. Synthetic
organic chemistry provides essentially an unlimited number of
degrees of freedom for tailoring molecular properties to achieve
specific functionality, from selective charge transport to
color-tunable light emission. The prospect of high-quality lighting
sources based on inexpensive "plastic" materials has driven a
tremendous amount of research in the area of OLEDs. which in turn
has led to the realization of several OLED-based high-tech products
such as flat screen televisions and mobile communication devices.
Several industrial giants such as Samsung, LG, Sony, and Panasonic
are working to develop large-area white-emitting OLEDs both for
lighting and display. Despite advances in the OLED field, there are
a few drawbacks of this technology that might prevent its
widespread use in commercial products. One problem is poor
cost-efficiency caused at least in part by the complexity of the
necessary device architecture, which requires multiple thermal
deposition steps during manufacture. Another problem is their
limited stability, particularly for deep-red and blue
phosphorescent OLEDs. While improving greatly in recent years, they
still do not meet the standards employed in high-end devices.
[0004] Chemically synthesized nanocrystal quantum dots (QDs) have
emerged as a promising class of emissive materials for low-cost yet
efficient LEDs. These luminescent nanomaterials feature
size-controlled tunable emission wavelengths and provide
improvements in color purity, stability and durability over organic
molecules. In addition, as with organic materials, colloidal QDs
can be fabricated and processed via inexpensive solution-based
techniques compatible with lightweight, flexible substrates.
Moreover, similar to other semiconductor materials, colloidal QDs
feature almost continuous above-band-edge absorption and a narrow
emission spectrum at near-band-edge energies. Distinct from bulk
semiconductors, however, the optical spectra of QDs depend directly
on their size. Specifically, their emission color can be
continuously tuned from the infrared (IR) to ultraviolet (UV) by
varying QD size and/or composition. The wide range spectral
tunability is combined with high photoluminescence (PL) quantum
yields (QYs) that approach unity in well-passivated structures.
These unique properties of QDs have been explored for use in
various devices such as LEDs, lasers, solar cells, and photo
detectors.
[0005] It is known that the quantum dots can degrade when they are
exposed in air and moisture. In presence of light, oxygen and
moisture molecules may cause photo-oxidation and photo-corrosion on
the surface of the quantum dots. Once quantum dots react with
oxygen and moisture, new defects may be created on the surface of
quantum dots. Such defects may result in decreased light emitting
of quantum dots.
[0006] In conventional quantum dot films, a quantum dot may be
disposed between a first barrier film and a second barrier film, as
illustrated in FIG. 1. Suitable barrier films include polymers
(e.g., PET); oxides such as silicon oxides, metal oxides, metal
nitrides, metal carbides, metal oxynitrides, and combinations
thereof. The barrier layers are typically formed using techniques
employed in the film metallizing art such as sputtering,
evaporation, chemical vapor deposition, plasma deposition, atomic
layer deposition, plating and the like. Second barrier film is
typically laminated on a quantum dot layer and often includes an
adhesion surface or layer. The thickness of each of the
conventional barrier layer is configured to eliminate wrinkling in
a roll-to-roll or laminate manufacturing processes, as may be
required by conventional methods described above.
[0007] Improvements in quantum dot films and methods of making the
same, are needed.
SUMMARY
[0008] A film for light emitting devices is disclosed. According to
one example, the film is formed from a process comprising disposing
a quantum dot solution between a first layer and a second layer;
wherein at least one of the first layer and the second layer is a
protective layer including a barrier polymer and a scavenger, the
scavenger absorbing at least one of oxygen and water to prevent the
at least one of oxygen and water from reacting with the quantum dot
solution; curing the quantum dot solution to form a film having a
stacked construction with a quantum dot layer between the first
layer and the second layer.
[0009] According to an example, an article comprising a first layer
and a second layer; a quantum dot layer disposed between the first
layer and the second layer; and wherein at least one of the first
layer and the second layer is a protective layer, the protective
layer comprising a barrier polymer and a scavenger, wherein the
protective layer inhibits the permeation of at least oxygen and
moisture into the quantum dot layer.
[0010] According to a further example, the first layer and the
second layer are protective layers including the barrier polymer
and the scavenger. According to still another example, the film
includes a substrate and wherein the first layer is disposed on the
substrate, the quantum dot layer is disposed on the first layer
opposite the substrate, and the second layer is disposed on the
quantum dot layer opposite the first layer.
[0011] According to another example, the film further comprises a
diffuser layer applied to the protective layer, wherein the
diffuser layer is on a surface of the protective layer opposite the
quantum dot layer.
[0012] According to another example, the first layer is a barrier
layer comprising an inorganic layer disposed between a substrate
and an adhesion layer, wherein the quantum dot solution is disposed
on the first layer, and the second layer is the protective layer
and is applied to the quantum dot layer.
[0013] According to a further example, a film for light emitting
devices, the film formed from a process comprising disposing a
quantum dot solution between a first layer and a second layer,
where at least one of the first layer and second layer is a
protective layer; and wherein the protective layer is formed by
mixing a barrier polymer with a scavenger.
[0014] In yet another example, a method comprises: disposing a
quantum dot solution on a first layer; applying a second layer to
the quantum dot solution; wherein at least one of the first layer
and second layer are a protective layer formed by providing a
barrier polymer with a scavenger, wherein the scavenger absorbs at
least one of oxygen and water to inhibit the at least one of oxygen
and water from reacting with the quantum dot solution; and curing
the first layer, second layer and quantum dot solution to form a
film comprising a stack of the first layer, the quantum dot layer,
and the second layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The above-mentioned and other features and advantages of
this disclosure, and the manner of attaining them, will become
apparent and be better understood by reference to the following
description of one aspect of the disclosure in conjunction with the
accompanying drawings, wherein:
[0016] FIG. 1 is a schematic representation of a composite layered
structure according to aspects of the prior art.
[0017] FIG. 2 is a schematic representation of a composite layered
structure according to examples of the present disclosure.
[0018] FIG. 3 is a schematic representation of a composite layered
structure according to examples of the present disclosure.
[0019] FIG. 4 is a schematic representation of a composite layered
structure according to examples of the present disclosure.
[0020] FIG. 5 is a method flow diagram according to aspects of the
present disclosure.
[0021] FIG. 6 is a method flow diagram according to further aspects
of the present disclosure.
[0022] FIG. 7 is a method flow diagram according to yet further
aspects of the present disclosure.
DETAILED DESCRIPTION
[0023] The disclosure relates to quantum dot films and methods of
forming quantum dot films having reduced manufacturing complexity
and film thickness (e.g., less than 50 micrometers (microns,
.mu.m), less than 100 micron, or other endpoint thicknesses between
5 microns and 50 microns or between 5 and 100 microns), among other
aspects. A protective layer may be disposed adjacent a quantum dot
layer to protect the quantum dot layer from oxygen and moisture. As
an example, a at least one of the barrier layers of a conventional
multi-layer film may be replaced with the protective layer of the
present disclosure. The protective layer may include one or more
layers. In one example, the protective layer includes a barrier
polymer and a scavenger. In a further example, the protective layer
may include a functional layer such as a diffuser layer or a prism
disposed thereon. As a further example, the protective layer may
include an inorganic layer or a hybrid layer. In still another
example, the film includes a quantum dot solution disposed between
a first layer and a second layer, where at least one of the first
and second layers is a protective layer comprising a barrier
polymer and a scavenger. The scavenger in this example inhibits at
least one of oxygen and moisture i.e. water from reacting with the
quantum dot solution by absorbing the at least one of oxygen and
moisture. According to one example, the first layer is a barrier
film, and the quantum dot solution is disposed on the barrier film
and cured to form a quantum dot layer on a barrier film. The second
layer is the protective layer and is applied to the quantum dot
layer opposite the first layer. According to another example, the
barrier polymer and scavenger are applied to a substrate to form
the first layer and the quantum dot solution is disposed on the
first layer, and the second layer comprising the barrier polymer
and the scavenger is applied on the quantum dot layer such that
both the first layer and second layer are protective layers. Other
configurations may be used as the protective layer, as described
herein. While the present disclosure is not so limited, an
appreciation of various aspects of the disclosure will be gained
through a discussion of the examples provided below.
[0024] With reference to FIG. 1, a conventional quantum dot film
includes a quantum dot solution disposed between first and second
barrier films. The barrier films inhibit oxygen and moisture from
reacting with the quantum dot layer by providing a physical
barrier. However, these films are relatively thick and, thus,
greatly contribute to the overall thickness of the quantum dot film
by making up two thirds of the film thickness without additional
functional layers. Also, they are relatively expensive to
produce.
[0025] In accordance with the disclosure herein, at least one of
the first and second barrier films in the conventional quantum dot
film is replaced with a protective layer. The protective layer
includes a barrier polymer provided with a scavenger, where the
presence of the scavenger inhibits at least one of oxygen and
moisture i.e. water from reaching the quantum dot solution as
discussed more completely below. The protective layer of the
disclosure is thinner than barrier layer reducing the overall
thickness of quantum dot film, and may also reduce the cost of
producing the quantum dot film.
[0026] FIG. 2 is a schematic side elevation view of an illustrative
quantum dot (QD) film 200. In one or more examples, the QD film 200
includes a first layer 202, a second layer 204, and a quantum dot
layer 206 disposed between the first layer 202 and the second layer
204.
[0027] The quantum dot layer 206 may include a quantum dot solution
210 dispersed in a polymer material 212 such as acryl type, epoxy
type, or silicone type polymers, or combinations thereof. The
quantum dot layer 206 may include one or more populations of
quantum dot material 214. Exemplary quantum dots or quantum dot
material 214 emit green light and red light upon down-conversion of
blue primary light from the blue LED to secondary light emitted by
the quantum dots. The respective portions of red, green, and blue
light can be controlled to achieve a desired white point for the
white light emitted by a display device incorporating the quantum
dot film article. Suitable quantum dots 214 for use in quantum dot
film articles described herein include core/shell luminescent
nanocrystals including cadmium selenium CdSe/zinc sulfide ZnS,
indium phosphide InP/zinc sulfide ZnS, lead selenide PbSe/PbS,
cadmium selenide CdSe/cadmium sulfide CdS, cadmium telluride
CdTe/CdS or CdTe/ZnS. The quantum dot layer 206 can have any useful
amount of quantum dots 214. In many aspects the quantum dot layer
206 can have from about 0.05 wt % to about 5 wt % quantum dots. It
is understood that various intervening endpoints in the proposed
size ranges may be used. However, other loadings of quantum dots
214 may be used.
[0028] The quantum dot layer 206 may include scattering beads or
particles, schematically depicted at 216. The inclusion of
scattering particles results in a longer optical path length and
improved quantum dot absorption and efficiency. The particle size
is in a range from 50 nanometers (nm) to 10 micrometers, or from
100 nm to 6 micrometers. It is understood that various intervening
endpoints in the proposed size ranges may be used. The quantum dot
layer 206 may include fillers such as fumed silica.
[0029] The first layer 202 may be formed of any useful material
that can protect the quantum dots from environmental conditions
such as oxygen and moisture. As discussed in more detail below, at
least one of the first layer 202 and second layer 204 may be a
protective layer 400.
[0030] In the example shown in FIG. 2, first layer 202 is a barrier
film 300. Suitable barrier films include polymers, glass or
dielectric materials, for example. Suitable barrier film materials
include, but are not limited to, polymers such as polyethylene
terephthalate (PET); oxides such as silicon oxide, titanium oxide,
or aluminum oxide (e.g., SiO.sub.2, Si.sub.2O.sub.3, TiO.sub.2, or
Al.sub.2O.sub.3); and suitable combinations thereof.
[0031] With reference to FIG. 3, the barrier layer 300 of the QD
film 200 may include at least two layers of different materials or
compositions, such that the multi-layered barrier eliminates or
reduces pinhole defect alignment in the barrier layer, providing an
effective barrier to oxygen and moisture penetration into the
quantum dot layer 206. The QD film 200 may include any suitable
material or combination of materials. In the examples shown in
FIGS. 2(a) and 2(b), only one barrier layer is provided, however,
additional barrier layers may be added outward of the structures
shown in the figures if desired for a particular QD film
application.
[0032] FIG. 3 illustrates an example barrier layer 300, which may
be embodied as the first layer 202 (FIG. 2). As shown, the barrier
layer 300 may include an inorganic layer 306 disposed on a base
substrate 304 (e.g., polymer). Optionally, a diffuser layer 302 may
be provided on substrate 304 opposite inorganic layer 306. The
inorganic layer 306 may include inorganic material such as a
polysilazane-based polymer, a polysiloxane-based polymer. The
inorganic layer may include oxides such as silicon oxide, titanium
oxide, or aluminum oxide (e.g., SiO.sub.2, Si.sub.2O.sub.3,
TiO.sub.2, or Al.sub.2O.sub.3); and suitable combinations thereof.
In certain aspects, a coating 308 may be applied, for example,
adjacent the inorganic layer 306. The coating 308 may be an
adhesive coating (e.g., organic layer) and may improve the adhesion
property with a QD layer, for example.
[0033] FIG. 4 illustrates an example protective layer 400, which
may be embodied as at least one of the first layer 202 and second
layer 204. In the example shown in FIG. 2, second layer 204 is a
protective layer 400. As shown in FIG. 4, the protective layer 400
may include a barrier polymer 401 combined with a scavenger 403.
Barrier polymer 401 may be any polymer suitably used in a barrier
film as described above. For example, barrier polymer 401 may
include inorganic material used such as a polysilazane-based
polymer, a polysiloxane-based polymer. As one non-limiting example,
the conversion of the material may be performed according to the
following reaction:
##STR00001##
[0034] In addition, barrier polymer may include organic and
inorganic hybrid materials. For example, the following structure
may be used, where R1 is an organic component offering flexibility
and R2 is an organic component that improves adhesion.
##STR00002##
[0035] Scavenger 403 may be any compound that absorbs at least one
of oxygen and moisture. For example, scavenger 403 may be a
phenolic acid. Phenolic acids are types of aromatic acid compound.
Included in that class are substances containing a phenolic ring
and an organic carboxylic acid function (C6-C1 skeleton). Phenolic
acids generally act as antioxidants by trapping free radicals.
Phenolic acids will be used as scavenger 403 which reacts with
oxygen and/or moisture in protecting layer 400. Phenolic acids can
prevent permeation of at least one of oxygen and moisture from
external atmosphere into quantum dot layer. There are several
categories of phenolic acids including:
##STR00003##
[0036] According to one example, scavenger 403 included a
protocatechuic acid. The reaction of protocatechuic acid with
oxygen and moisture is representative of use of a phenolic acid as
a scavenger according to the examples herein, as shown below:
##STR00004##
[0037] Optionally, protective layer 400 may include a functional
layer 402. For example, functional layer 402 may be or include a
diffuser layer 405 (FIG. 2(b)). Diffuser layer 405 may be applied
on a side 404 of protective layer 400 opposite of quantum dot layer
206. In another example, functional layer 402 is a prism 407 (FIG.
4) to enhance brightness of the underlying film. Other functional
or ornamental layers may be used such as a surface matt treatment
and/or scratch resistant treatment as desired for a given
application of film 200.
[0038] With reference to FIG. 2(b), according to another example,
film 200 may include a functional layer 402 that is applied to one
or more of the protective layers outward of quantum dot layer.
Functional layer 402 may be applied to second layer 204 on a side
of second layer opposite quantum dot layer. In this example, second
layer 204 is a protective layer 400. Functional layer 402 may be a
diffuser layer as schematically shown. Other functional or
ornamental layers may be used such as surface matt treatment and/or
scratch resistant treatment as desired for a given application of
film 200
[0039] The protecting layer 400 may be formed by low temperature
wet processes. As an example, the protective layer according to
aspects of the present disclosure may be or comprise a flowable
curable coating composition as described herein. As such, the
flowable curable coating composition may be used to coat a surface
such as a quantum dot layer 206 of a film 200. As an example, a low
temperature wet process may include a coating method including but
not limited to roll coating, gravure coating, knife coating, dip
coating, curtain flow coating, spray coating, bar coating, die
coating, spin coating, or inkjet coating and the like.
[0040] Once the protective layer is applied to the quantum dot
layer 206, protective layer 400 may be separately cured according
to curing methods appropriate for the material including but not
limited to ultraviolet (UV) curing. As an illustrative example,
ultraviolet (UV) curing may be performed in a gastight aluminum
casing equipped with low pressure mercury lamps (Hg LP; Heraeus
Noblelight NIQ 65XL). The lamps may be configured to emit in the UV
domain at about 254 nm (20 watts, W) and in the vacuum ultraviolet
(VUV) domain at about 185 nm (5 W) with a distance to the sample at
20 mm. A gas sweeping may be applied and may include a mixture of
99.9% pure dry nitrogen and 5% O.sub.2 in dry nitrogen. Before
beginning the curing of the sample, atmosphere may be purged with
nitrogen during 10 min (8 liters per minute, L/min) and lamps may
be allowed to heat to nominal power. The curing may occur with a
partial pressure of oxygen at the surface of the sample inferior or
equal to 1%.
[0041] With reference to FIG. 2C, a film 200 where both the first
layer and second layer are protective layers is shown. In this
example, first layer includes a substrate to which the protective
solution is applied. Quantum dot solution may then be disposed on
the first protective layer and cured. The second layer, which is
also a protective layer, is then applied to quantum dot solution as
discussed above. In the example shown, first protective layer is
disposed on a substrate and cured to form first layer of film 200.
A curable protective layer coating composition can be cured to
provide a hardened film on the solid plastic form surface. The
hardened film can provide an abrasion resistant coating layer. The
hardened film can provide high surface hardness and a glass-like
feel, and can provide a desirable combination of properties such as
hardness, scratch resistance, mechanical strength, and impact
resistance. A filler, polyester, or combination thereof, can
produce a surprising increase in hardness as compared to the
results of the treatment as performed on a solid plastic form free
of filler and polyester.
[0042] The method can include coating a surface of a solid plastic
form with a flowable curable coating composition. The coating can
be performed in any suitable manner that forms a coating of the
flowable curable coating composition on a surface of the solid
plastic form. Wet or transfer coating methods can be used. For
example, the coating can be bar coating, spin coating, spray
coating, or dipping. Single- or multiple-side coating can be
performed.
[0043] The solid plastic form can be transparent, opaque, or any
one or more colors. The solid plastic form can include any one or
more suitable plastics (e.g., as a homogeneous mixture of
plastics). In some aspects, the solid plastic form can include at
least one of an acrylonitrile butadiene styrene (ABS) polymer, an
acrylic polymer, a celluloid polymer, a cellulose acetate polymer,
a cycloolefin copolymer (COC), an ethylene-vinyl acetate (EVA)
polymer, an ethylene vinyl alcohol (EVOH) polymer, a fluoroplastic,
an ionomer, an acrylic/PVC alloy, a liquid crystal polymer (LCP), a
polyacetal polymer (POM or acetal), a polyacrylate polymer, a
polymethylmethacrylate polymer (PMMA), a polyacrylonitrile polymer
(PAN or acrylonitrile), a polyamide polymer (PA or nylon), a
polyamide-imide polymer (PAI), a polyaryletherketone polymer
(PAEK), a polybutadiene polymer (PBD), a polybutylene polymer (PB),
a polybutylene terephthalate polymer (PBT), a polycaprolactone
polymer (PCL), a polychlorotrifluoroethylene polymer (PCTFE), a
polytetrafluoroethylene polymer (PTFE), a polyethylene
terephthalate polymer (PET), a polycyclohexylene dimethylene
terephthalate polymer (PCT), a polycarbonate polymer (PC), a
polyhydroxyalkanoate polymer (PHA), a polyketone polymer (PK), a
polyester polymer, a polyethylene polymer (PE), a
polyetheretherketone polymer (PEEK), a polyetherketoneketone
polymer (PEKK), a polyetherketone polymer (PEK), a polyetherimide
polymer (PEI), a polyethersulfone polymer (PES), a
polyethylenechlorinate polymer (PEC), a polyimide polymer (PI), a
polylactic acid polymer (PLA), a polymethylpentene polymer (PMP), a
polyphenylene oxide polymer (PPO), a polyphenylene sulfide polymer
(PPS), a polyphthalamide polymer (PPA), a polypropylene polymer, a
polystyrene polymer (PS), a polysulfone polymer (PSU), a
polytrimethylene terephthalate polymer (PTT), a polyurethane
polymer (PU), a polyvinyl acetate polymer (PVA), a polyvinyl
chloride polymer (PVC), a polyvinylidene chloride polymer (PVDC), a
polyamideimide polymer (PAI), a polyarylate polymer, a
polyoxymethylene polymer (POM), and a styrene-acrylonitrile polymer
(SAN). In some aspects, the solid plastic form includes at least
one of polycarbonate polymer (PC) and polymethylmethacrylate
polymer (PMMA). The solid plastic form can include a blend of PC
and PMMA.
[0044] The solid plastic form can include one type of polycarbonate
or multiple types of polycarbonate. The polycarbonate can be made
via interfacial polymerization (e.g., reaction of bisphenol with
phosgene at an interface between an organic solution such as
methylene chloride and a caustic aqueous solution) or melt
polymerization (e.g., transesterification and/or polycondensation
of monomers or oligomers above the melt temperature of the reaction
mass). Although the reaction conditions for interfacial
polymerization may vary, in an example the procedure can include
dissolving or dispersing a dihydric phenol reactant in aqueous
caustic soda or potash, adding the resulting mixture to a suitable
water-immiscible solvent medium, and contacting the reactants with
a carbonate precursor (e.g., phosgene) in the presence of a
catalyst such as triethylamine or a phase transfer catalyst, under
controlled pH conditions, e.g., about 8 to about 10. The most
commonly used water-immiscible solvents include methylene chloride,
1,2-dichloroethane, chlorobenzene, toluene, and the like.
[0045] Alternatively, melt processes may be used to make the
polycarbonates. Generally, in the melt polymerization process,
polycarbonates may be prepared by co-reacting, in a molten state,
the dihydroxy reactant(s) and a diaryl carbonate ester, such as
diphenyl carbonate, in the presence of a transesterification
catalyst in a mixer, twin screw extruder, or the like, to form a
uniform dispersion. Volatile monohydric phenol can be removed from
the molten reactants by distillation and the polymer can be
isolated as a molten residue. In some aspects, a melt process for
making polycarbonates uses a diaryl carbonate ester having
electron-withdrawing substituents on the aryl groups, such as
bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate,
bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate,
bis(4-methylcarboxylphenyl)carbonate,
bis(2-acetylphenyl)carboxylate, bis(4-acetylphenyl)carboxylate, or
a combination thereof. In addition, transesterification catalysts
for use may include phase transfer catalysts such as
tetrabutylammonium hydroxide, methyltributylammonium hydroxide,
tetrabutylammonium acetate, tetrabutylphosphonium hydroxide,
tetrabutylphosphonium acetate, tetrabutylphosphonium phenolate, or
a combination thereof.
[0046] The one or more polycarbonates can be about 50 wt % to about
100 wt % of the solid plastic form, such as about 50 wt % or less,
or about 55 wt %, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99,
99.9 wt %, or about 99.99 wt % or more. In various aspects, the
polycarbonate can include a repeating group having the
structure:
##STR00005##
[0047] Each phenyl ring in the structure is independently
substituted or unsubstituted. The variable L.sup.3 is chosen from
--S(O).sub.2-- and substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbylene. In various aspects, the
polycarbonate can be derived from bisphenol A, such that the
polycarbonate includes a repeating group having the structure:
##STR00006##
[0048] The solid plastic form can include a filler, such as one
filler or multiple fillers. The filler can be any suitable type of
filler. The filler can be homogeneously distributed in the solid
plastic form. The one or more fillers can form about 0.001 wt % to
about 50 wt % of the solid plastic form, or about 0.01 wt % to
about 30 wt %, or about 0.001 wt % or less, or about 0.01 wt %,
0.1, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45 wt %, or about
50 wt % or more. The filler can be fibrous or particulate. The
filler can be aluminum silicate (mullite), synthetic calcium
silicate, zirconium silicate, fused silica, crystalline silica
graphite, natural silica sand, or the like; boron powders; oxides
such as TiO.sub.2, aluminum oxide, magnesium oxide, or the like;
calcium sulfate (as its anhydride, dehydrate or trihydrate);
calcium carbonates such as chalk, limestone, marble, synthetic
precipitated calcium carbonates, or the like; talc, including
fibrous, modular, needle shaped, lamellar talc, or the like;
wollastonite; surface-treated wollastonite; glass spheres such as
hollow and solid glass spheres; kaolin; single crystal fibers or
"whiskers" such as silicon carbide, alumina, boron carbide, iron,
nickel, copper, or the like; fibers (including continuous and
chopped fibers) such as asbestos, carbon fibers, glass fibers;
sulfides such as molybdenum sulfide, zinc sulfide, or the like;
barium compounds; metals and metal oxides such as particulate or
fibrous materials; flaked fillers; fibrous fillers, for example
short inorganic fibers such as those derived from blends including
at least one of aluminum silicates, aluminum oxides, magnesium
oxides, and calcium sulfate hemihydrate or the like; natural
fillers and reinforcements; organic fillers such as
polytetrafluoroethylene, reinforcing organic fibrous fillers formed
from organic polymers capable of forming fibers such as poly(ether
ketone), polyimide, polybenzoxazole, poly(phenylene sulfide),
polyesters, polyethylene, aromatic polyamides, aromatic polyimides,
polyetherimides, polytetrafluoroethylene, acrylic resins,
poly(vinyl alcohol) or the like; or combinations including at least
one of the foregoing fillers. The filler can be selected from glass
fibers, carbon fibers, a mineral fillers, or combinations thereof.
The filler can be glass fibers.
[0049] The glass fibers can be selected from E-glass, S-glass,
AR-glass, T-glass, D-glass, R-glass, and combinations thereof. The
glass fibers used can be selected from E-glass, S-glass, and
combinations thereof. High-strength glass is generally known as
S-type glass in the United States, R-glass in Europe, and T-glass
in Japan. High-strength glass has appreciably higher amounts of
silica oxide, aluminum oxide and magnesium oxide than E-glass. S-2
glass is approximately 40-70% stronger than E-glass. The glass
fibers can be made by standard processes, e.g., by steam or air
blowing, flame blowing, and mechanical pulling.
[0050] The glass fibers can be sized or unsized. Sized glass fibers
are coated on their surfaces with a sizing composition selected for
compatibility with the polycarbonate. The sizing composition
facilitates wet-out and wet-through of the polycarbonate on the
fiber strands and assists in attaining desired physical properties
in the polycarbonate composition. The glass fibers can be sized
with a coating agent. The coating agent can be present in an amount
from about 0.1 wt % to about 5 wt %, or about 0.1 wt % to about 2
wt %, based on the weight of the glass fibers.
[0051] In preparing the glass fibers, a number of filaments can be
formed simultaneously, sized with the coating agent and then
bundled into what is called a strand. Alternatively the strand
itself may be first formed of filaments and then sized. The amount
of sizing employed is generally that amount which is sufficient to
bind the glass filaments into a continuous strand and can be about
0.1 to about 5 wt %, about 0.1 to 2 wt %, or about 1 wt %, based on
the weight of the glass fibers.
[0052] The glass fibers can be continuous or chopped. Glass fibers
in the form of chopped strands may have a length of about 0.3
millimeters (mm) to about 10 centimeters (cm), about 0.5 cm to
about 5 cm, or about 1.0 mm to about 2.5 cm. In various further
aspects, the glass fibers can have a length of about 0.2 mm to
about 20 mm, about 0.2 mm to about 10 mm, or about 0.7 mm to about
7 mm, 1 mm or longer, or 2 mm or longer. The glass fibers can have
a round (or circular), flat, or irregular cross-section. The
diameter of the glass fibers can be about 1 .mu.m to about 15
.mu.m, about 4 to about 10 .mu.m, about 1 .mu.m to about 10 .mu.m,
or about 7 .mu.m to about 10 .mu.m.
[0053] The solid plastic form can include a polyester. The
polyester can be any suitable polyester. The polyester can be
chosen from aromatic polyesters, poly(alkylene esters) including
poly(alkylene arylates) (e.g., poly(alkylene terephthalates)), and
poly(cycloalkylene diesters) (e.g., poly(cyclohexanedimethylene
terephthalate) (PCT), or
poly(1,4-cyclohexane-dimethanol-1,4-cyclohexanedicarboxylate)
(PCCD)), and resorcinol-based aryl polyesters. The polyester can be
poly(isophthalate-terephthalate-resorcinol)esters,
poly(isophthalate-terephthalate-bisphenol A)esters,
poly[(isophthalate-terephthalate-resorcinol)ester-co-(isophthalate-tereph-
thalate-bisphenol A)]ester, or a combination including at least one
of these. Examples of poly(alkylene terephthalates) include
poly(ethylene terephthalate) (PET), poly(1,4-butylene
terephthalate) (PBT), and poly(propylene terephthalate) (PPT). Also
useful are poly(alkylene naphthoates), such as poly(ethylene
naphthanoate) (PEN), and poly(butylene naphthanoate) (PBN).
Copolymers including alkylene terephthalate repeating ester units
with other ester groups can also be useful. Useful ester units can
include different alkylene terephthalate units, which can be
present in the polymer chain as individual units, or as blocks of
poly(alkylene terephthalates). Specific examples of such copolymers
include poly(cyclohexanedimethylene terephthalate)-co-poly(ethylene
terephthalate), abbreviated as PETG where the polymer includes
greater than or equal to 50 mol % of poly(ethylene terephthalate),
and abbreviated as PCTG where the polymer includes greater than 50
mol % of poly(1,4-cyclohexanedimethylene terephthalate). The
polyester can be substantially homogeneously distributed in the
solid plastic form. The solid plastic form can include one type of
polyester or multiple types of polyester. The one or more
polyesters can form any suitable proportion of the solid plastic
form, such as about 0.001 wt % to about 50 wt % of the solid
plastic form, about 0.01 wt % to about 30 wt %, or about 0.001 wt %
or less, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14,
16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45 wt %, or about 50 wt %
or more. The polyester can includes a repeating unit having the
structure:
##STR00007##
The variables R.sup.8 and R.sup.9 can be independently substituted
or unsubstituted (C.sub.1-C.sub.20)hydrocarbylene. The variables
R.sup.8 and R.sup.9 can be cycloalkylene-containing groups or
aryl-containing groups. The variables R.sup.8 and R.sup.9 can be
independently substituted or unsubstituted phenyl, or substituted
or unsubstituted
--(C.sub.0-C.sub.10)hydrocarbyl-(C.sub.4-C.sub.10)cycloalkyl-(C.sub.0-C.s-
ub.10)hydrocarbyl-. The variables R.sup.8 and R.sup.9 can both be
cycloalkylene-containing groups. The variables R.sup.8 and R.sup.9
can independently have the structure:
##STR00008##
wherein the cyclohexylene can be substituted in a cis or trans
fashion. In some examples, R9 can be a para-substituted phenyl,
such that R.sup.9 appears in the polyester structure as:
##STR00009##
[0054] The solid plastic form can have any suitable shape and size.
In some aspects, the solid plastic form is a sheet having any
suitable thickness, such as a thickness of about 25 microns to
about 50,000 microns, about 25 microns to about 15,000 microns,
about 60 microns to about 800 microns, or about 25 microns or less,
or about 50, 75, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800,
900, 1,000, 1,500, 2,000, 3,000, 4,000, 5,000, 6,000, 8,000,
10,000, 12,000, 14,000, 15,000, 20,000, 25,000, 30,000, 40,000, or
about 50,000 microns or more.
[0055] The flowable curable coating composition can include a) an
alicyclic epoxy group-containing siloxane resin having a weight
average molecular weight of about 1,000 to about 4,000 and a
(M.sub.w/M.sub.n) of about 1.05 to about 1.4, b) an
epoxy-functional organosiloxane and an organosiloxane comprising a
isocyanate group or an isocyanurate group, or both a) and b).
[0056] The epoxy-functional oganosiloxane can have the
structure:
##STR00010##
At each occurrence, R.sup.a can be independently substituted or
unsubstituted (C.sub.1-C.sub.10)alkyl. At each occurrence, the
variable R can be independently unsubstituted
(C.sub.1-C.sub.6)alkyl. The variable La can be substituted or
unsubstituted (C.sub.1-C.sub.30)hydrocarbyl interrupted by 0, 1, 2,
or 3 groups independently chosen from --O--, --S--, substituted or
unsubstituted --NH--, --(Si(OR.sup.a).sub.2).sub.n1--,
--(O--CH.sub.2--CH.sub.2).sub.n1--, and
--(O--CH.sub.2--CH.sub.2--CH.sub.2).sub.n1--, wherein n can be
about 1 to about 1,000 (e.g., 1-100, 1-50, 1-10, 1, 2, 3, 4, 5, 6,
8, 10, 12, 14, 16, 18, 20, 25, 30, 40, 50, 75, 100, 200, 250, 500,
750, 1,000). The variable La can be an unsubstituted
(C.sub.1-C.sub.30)hydrocarbyl interrupted by 0, 1, 2, or 3 groups
independently chosen from --O-- and --S--. The epoxy-functional
organosiloxane can be 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl
trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, or
3-glycidoxypropyl triethoxysilane. The flowable curable resin
composition can include one epoxy-functional organosiloxane, or
multiple epoxy-functional organosiloxanes. The one or more
epoxy-functional organosiloxanes can be any suitable proportion of
the flowable curable resin composition such as about 0.01 wt % to
about 100 wt %, 10 wt % to about 100 wt %, about 50 wt % to about
99.9 wt %, or about 0.01 wt % or less, or about 0.1 wt %, 1, 2, 3,
4, 5, 6, 8, 10, 12, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65,
70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, or about 99.99 wt
%.
[0057] The organosiloxane including an isocyanate group can have
the structure (R.sup.b).sub.4-pSi(R.sup.c).sub.p. The variable p
can be 1 to 4 (e.g., 1, 2, 3, or 4). At each occurrence, R.sup.b
can be independently chosen from substituted or unsubstituted
(C.sub.1-C.sub.10)alkyl and substituted or unsubstituted
(C.sub.1-C.sub.10)alkoxy. At each occurrence, R.sup.b can be
independently chosen from unsubstituted (C.sub.1-C.sub.6)alkyl and
unsubstituted (C.sub.1-C.sub.6)alkoxy. At each occurrence, R.sup.c
can be -L.sup.b-NCO, wherein L.sup.b can be a substituted or
unsubstituted (C.sub.1-C.sub.30)hydrocarbyl interrupted by 0, 1, 2,
or 3 groups independently chosen from --O--, --S--, substituted or
unsubstituted --NH--, --(Si(OR.sup.b).sub.2).sub.n2--,
--(O--CH.sub.2--CH.sub.2).sub.n2--, and
--(O--CH.sub.2--CH.sub.2--CH.sub.2).sub.n2--, wherein n2 can be
about 1 to about 1,000 (e.g., 1-100, 1-50, 1-10, 1, 2, 3, 4, 5, 6,
8, 10, 12, 14, 16, 18, 20, 25, 30, 40, 50, 75, 100, 200, 250, 500,
750, 1,000). At each occurrence, LE can be an unsubstituted
(C.sub.1-C.sub.30)hydrocarbyl interrupted by 0, 1, 2, or 3 groups
independently chosen from --O-- and --S--. The organosiloxane
including the isocyanate group can be
3-isocyanatepropyltriethoxysilane. The flowable curable resin
composition can include one or more than one organosiloxane
including an isocyanate group. The one or more organosiloxanes
including an isocyanate group can form any suitable proportion of
the flowable curable resin composition, such as about 0.01 wt % to
about 100 wt %, 10 wt % to about 100 wt %, about 50 wt % to about
99.9 wt %, or about 0.01 wt % or less, or about 0.1 wt %, 1, 2, 3,
4, 5, 6, 8, 10, 12, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65,
70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, or about 99.99 wt
%.
[0058] The organosiloxane including an isocyanurate group can have
the structure:
##STR00011##
At each occurrence, R.sup.d can be chosen from --H and
-L.sup.c-Si(R.sup.e).sub.3, wherein at least one R.sup.d is
-L.sup.c-Si(R.sup.e).sub.3. At each occurrence, R.sup.d can be
-L.sup.c-Si(R.sup.e).sub.3. At each occurrence, LE can be
independently a substituted or unsubstituted
(C.sub.1-C.sub.30)hydrocarbyl interrupted by 0, 1, 2, or 3 groups
independently chosen from --O--, --S--, substituted or
unsubstituted --NH--, --(Si(R.sup.e).sub.2).sub.n3--,
--(O--CH.sub.2--CH.sub.2).sub.n3--, and
--(O--CH.sub.2--CH.sub.2--CH.sub.2).sub.n3--, wherein n3 can be
about 1 to about 1,000 (e.g., 1-100, 1-50, 1-10, 1, 2, 3, 4, 5, 6,
8, 10, 12, 14, 16, 18, 20, 25, 30, 40, 50, 75, 100, 200, 250, 500,
750, 1,000). At each occurrence, LE can be an unsubstituted
(C.sub.1-C.sub.30)hydrocarbyl interrupted by 0, 1, 2, or 3 groups
independently chosen from --O-- and --S--. At each occurrence, R
can be chosen from substituted or unsubstituted
(C.sub.1-C.sub.10)alkyl and substituted or unsubstituted
(C.sub.1-C.sub.10)alkoxy. At each occurrence, R can be
independently chosen from unsubstituted (C.sub.1-C.sub.6)alkyl and
unsubstituted (C.sub.1-C.sub.6)alkoxy. The organosiloxane including
the isocyanate group or isocyanurate group can be
tris-[3-(trimethoxysilyl propyl)-isocyanurate. The flowable curable
resin composition can include one or multiple organosiloxanes
including an isocyanurate group. Any suitable proportion of the
flowable curable resin composition can be the one or more
organosiloxanes including an isocyanurate group, such as about 0.01
wt % to about 100 wt %, 10 wt % to about 100 wt %, about 50 wt % to
about 99.9 wt %, or about 0.01 wt % or less, or about 0.1 wt %, 1,
2, 3, 4, 5, 6, 8, 10, 12, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55,
60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, or about
99.99 wt %.
[0059] The flowable curable resin composition can include a
bis(organosiloxane)-functional amine. In some aspects, the flowable
curable resin composition includes an epoxy-functional
organosiloxane, an organosiloxane comprising a isocyanate group or
an isocyanurate group, and a bis(organosiloxane)-functional amine.
The bis(organosiloxane)-functional amine can have the structure
R.sup.f.sub.3Si-L.sup.d-NH-L.sup.d-SiR.sup.f.sub.3. At each
occurrence, R.sup.f can be chosen from substituted or unsubstituted
(C.sub.1-C.sub.10)alkyl and substituted or unsubstituted
(C.sub.1-C.sub.10)alkoxy. At each occurrence, R.sup.f can be
independently chosen from unsubstituted (C.sub.1-C.sub.6)alkyl and
unsubstituted (C.sub.1-C.sub.6)alkoxy. At each occurrence, L.sup.d
can be independently a substituted or unsubstituted
(C.sub.1-C.sub.30)hydrocarbyl interrupted by 0, 1, 2, or 3 groups
independently chosen from --O--, --S--, substituted or
unsubstituted --NH--, --(Si(R.sup.f).sub.2).sub.n4--,
--(O--CH.sub.2--CH.sub.2).sub.n4--, and
--(O--CH.sub.2--CH.sub.2--CH.sub.2).sub.n4--, wherein n4 can be
about 1 to about 1,000 (e.g., 1-100, 1-50, 1-10, 1, 2, 3, 4, 5, 6,
8, 10, 12, 14, 16, 18, 20, 25, 30, 40, 50, 75, 100, 200, 250, 500,
750, 1,000). At each occurrence, L.sup.d can be an unsubstituted
(C.sub.1-C.sub.30)hydrocarbyl interrupted by 0, 1, 2, or 3 groups
independently chosen from --O-- and --S--. The
bis(organosiloxane)-functional amine can be
bis(triethoxysilylpropyl)amine, bis(trimethoxysilylpropyl)amine, or
bis(methyldiethoxysilylpropyl) amine. The flowable curable resin
composition can include one or more bis(organosiloxane)-functional
amines. The one or more bis(organosiloxane)-functional amines can
form any suitable proportion of the flowable curable resin
composition, such as about 0.01 wt % to about 100 wt %, 10 wt % to
about 100 wt %, about 50 wt % to about 99.9 wt %, or about 0.01 wt
% or less, or about 0.1 wt %, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 15,
20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96,
97, 98, 99, 99.9, or about 99.99 wt %.
[0060] The method can include performing a hydrolysis and
condensation reaction using water and a catalyst to form a sol
(e.g., colloidal suspension), releasing alcohol or water. The sol
can include the flowable curable resin composition. Coating the
surface of the solid plastic form can include coating the solid
plastic form with the sol. Curing the curable coating composition
can include curing the sol on the plastic form, to provide the
hardened film (e.g., gel) on the solid plastic form surface.
[0061] The flowable curable coating composition can include an
alicyclic epoxy group-containing siloxane resin. The flowable
curable coating composition can include one type of alicyclic epoxy
group-containing siloxane resin or multiple types of such resin.
The one or more alicyclic epoxy group-containing siloxane resin can
form any suitable proportion of the flowable curable coating
composition, such as about 0.01 wt % to about 100 wt %, 10 wt % to
about 100 wt %, about 50 wt % to about 99.9 wt %, or about 0.01 wt
% or less, or about 0.1 wt %, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 15,
20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96,
97, 98, 99, 99.9, or about 99.99 wt %. The siloxane resin can have
a weight average molecular weight of about 1,000 to about 4,000
(e.g., about 1,000, 1,200, 1,400, 1,600, 1,800, 2,000, 2,200,
2,400, 2,600, 2,800, 3,000, 3,200, 3,400, 3,600, 3,800, or 4,000)
and a (M.sub.w/M.sub.n) (i.e., weight average molecular weight
divided by number average molecular weight, also referred to as
polydispersity, a measure of the heterogeneity of sizes of
molecules in the mixture) of about 1.05 to about 1.4 (e.g., about
1.05, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4,
3.6, 3.8, or about 4.0 or more).
[0062] The siloxane resin can be prepared by hydrolysis and
condensation, in the presence of water and an optional catalyst, of
(i) an alkoxysilane including an alicyclic epoxy group and an
alkoxy group having the structure R.sup.1.sub.nSi(OR.sup.2).sub.4-n
alone, wherein R.sup.1 is
(C.sub.3-C.sub.6)cycloalkyl(C.sub.1-C.sub.6)alkyl wherein the
cycloalkyl group includes an epoxy group, R.sup.2 is (C1-C7)alkyl,
and n is 1-3, or (ii) the alkoxysilane having the structure
R.sup.1.sub.nSi(OR.sup.2).sub.4-n and an alkoxysilane having the
structure R.sup.3.sub.mSi(OR.sup.4).sub.4-m, wherein R.sup.3 is
chosen from (C.sub.1-C.sub.20)alkyl, (C.sub.3-C.sub.8)cycloalkyl,
(C.sub.2-C.sub.20)alkenyl, (C.sub.2-C.sub.20)alkynyl,
(C.sub.6-C.sub.20)aryl, an acryl group, a methacyl group, a halogen
group, an amino group, a mercapto group, an ether group, an ester
group, a carbonayl group, a carboxyl group, a vinyl group, a nitro
group, a sulfone group, and an alkyd group, R.sup.4 is
(C.sub.1-C.sub.7)alkyl, and m is 0 to 3. The alkoxysilxane having
the structure R.sup.1.sub.nSi(OR.sup.2).sub.4-n can be
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane or
2-(3,4-epoxycyclohexyl)ethyltriethoxysilane. The alkoxysilane
having the structure R.sup.3.sub.mSi(OR.sup.4).sub.4-m can be one
or more chosen from tetramethoxysilane, tetraethoxysilane,
methyltrimethoxysilane, methyltriethoxysilane,
methyltripropoxysilane, dimethyldimethoxysilane,
dimethyldiethoxysilane, phenyltrimethoxysilane,
phenyltriethoxysilane, diphenyldimethoxysilane,
diphenyldiethoxysilane, triphenylmethoxysilane,
triphenylethoxysilane, ethyltriethoxysilane,
propylethyltrimethoxysilane, vinyltrimethoxysilane,
vinyltriethoxysilane, vinyltripropoxysilane,
N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltrimethoxysilane,
N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,
N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltripropoxysilane,
3-acryloxypropylmethylbis (trimethoxy) silane,
3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane,
3-acryloxypropyltripropoxysilane,
3-(meth)acryloxypropyltrimethoxysilane,
3-(meth)acryloxypropyltriethoxysilane,
3-(meth)acryloxypropyltripropoxysilane,
N-(aminoethyl-3-aminopropyl)trimethoxysilane,
N-(2-aminoethyl-3-aminopropyl)triethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
chloropropyltrimethoxysilane, chloropropyltriethoxysilane, and
heptadecafluorodecyltrimethoxysilane.
[0063] The flowable curable coating composition can further include
a reactive monomer capable of reacting with the alicyclic epoxy
group to form crosslinking. The flowable curable coating
composition can include one such monomer or multiple such monomers.
The one or more reactive monomers can form any suitable proportion
of the flowable curable coating composition, such as about 0.001 wt
% to about 30 wt %, or about 0.01 wt % to about 10 wt %, or about
0.001 wt % or less, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8,
10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or about 30 wt % or more.
The one or more reactive monomer can be present in any suitable
weight ratio to the epoxy-containing siloxane resin, such as about
1:1000 to about 1:10, or about 1:1000 or less, or about 1:500,
1:250, 1:200, 1:150, 1:100, 1:80, 1:60, 1:40, 1:20, or about 1:10
or more. The reactive monomer can be an acid anhydride monomer, an
oxetane monomer, or a monomer having an alicyclic epoxy group as a
(C.sub.3-C.sub.6)cycloalkyl group. The acid anhydride monomer can
be one or more chosen from phthalic anhydride, tetrahydrophthalic
anhydride, hexahydrophthalic anhydride, nadic methyl anhydride,
chlorendic anhydride, and pyromellitic anhydride. The oxetane
monomer can be one or more chosen from
3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylene bis
oxetane, and 3-ethyl-3[[3-ethyloxetan-3-yl]methoxy]oxetane. The
reactive monomer having an alicyclic epoxy group can be one or more
chosen from 4-vinylcycloghexene dioxide, cyclohexene vinyl
monoxide, (3,4-epoxycyclohexyl)methyl
3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylmethyl
methacrylate, and bis(3,4-epoxycyclohexylmethyl)adipate.
[0064] In various aspects, one or more catalysts are present. In
other aspects, the flowable curable coating composition can be free
of catalyst. The catalyst can be any suitable catalyst, such as
acidic catalysts, basic catalysts, ion exchange resins, and
combinations thereof. For example, the catalyst can be hydrochloric
acid, acetic acid, hydrogen fluoride, nitric acid, sulfuric acid,
chlorosulfonic acid, iodic acid, pyrophosphoric acid, ammonia,
potassium hydroxide, sodium hydroxide, barium hydroxide, imidazole,
and combinations thereof.
[0065] The curable flowable coating composition can include one or
more organic solvents, such as in an amount of about 0.01 to about
10 parts by weight, based on 100 parts by weight of the siloxane
resin, or about 0.1 to about 10 parts by weight. The one or more
solvents can be about 0.001 wt % to about 50 wt % of the curable
flowable coating composition, about 0.01 wt % to about 30 wt %,
about 30 wt % to about 70 wt/%, or about 0.001 wt % or less, or
about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20,
22, 24, 26, 28, 30, 35, 40, 45 wt %, or about 50 wt % or more.
[0066] The flowable curable coating composition can further
includes one or more polymerization initiators chosen from UV
initiators, thermal initiators, onium salts, organometallic salts,
amines, and imidazoles in an amount of about 0.01 to about 10 parts
by weight, based on 100 parts by weight of the siloxane resin, or
about 0.1 to about 10 parts by weight. The one or more
polymerization initiators can be about 0.001 wt % to about 50 wt %
of the curable flowable coating composition, about 0.01 wt % to
about 30 wt %, or about 0.001 wt % or less, or about 0.01 wt %,
0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28,
30, 35, 40, 45 wt %, or about 50 wt % or more.
[0067] The flowable curable coating composition can further include
one or more additives, such as chosen from an antioxidant, a
leveling agent, an antifogging agent, an antifouling agent, and a
coating control agent. According to the disclosure, a scavenger is
provided within the flowable curable coating composition when
forming a protective layer. The scavenger inhibits at least one of
oxygen and moisture from contacting the quantum dot layer and
reacting with it.
[0068] The method can also include curing the curable coating
composition, to provide a hardened film on the solid plastic form
surface. The curing can be any suitable curing. The curing can be
thermal curing. The curing can be UV curing. The curing can be a
combination of thermal and UV curing (e.g., in parallel or
sequential).
[0069] The hardened film on the solid plastic form can have any
suitable thickness, such as about 1 micron to about 1,000 microns,
about 1 micron to about 100 microns, about 5 microns to about 75
microns, or about 1 micron, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18,
20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95,
100, 200, 500, 750, or about 1,000 microns or more.
[0070] The hardened film on the solid plastic form surface can have
any suitable hardness. For example, the hardened film on the solid
plastic form surface can have a hardness, namely a pencil hardness
of about 3B to about 9H, or about HB to about 8H, or about 3B or
less, or about 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, or
about 9H or more. Pencil hardness is a measure of the hardness of a
material on a scale ranging from 9H (hardest) to 9B (softest). In
general, the pencil hardness scale is 9H (hardest), 8H, 7H, 6H, 5H,
4H, 3H, 2H, H, F, HB (medium), B, 2B, 3B, 4B, 5B, 6B, 7B, 8B, and
9B (softest), for example, at a 700 grams (g) or 1 kg load. In an
aspect, the hardened film on the solid plastic form surface may
have a pencil hardness of about 3B to about 9H, or about HB to
about 8H, or about 3B or less, or about 2B, B, HB, F, H, 2H, 3H,
4H, 5H, 6H, 7H, 8H, or about 9H or more. Pencil hardness may be
determined according to ASTM D3363 at a 1 kg load, for example.
Methods of Making
[0071] In one or more aspects, and with reference to FIG. 2 for
example, a method of forming a quantum dot film 200 includes
coating a quantum dot solution on a first layer 202 and disposing a
second layer 204 on the quantum dot layer 206. However, other
process may be used. In the example, at least one of the first
layer and second layer is a protective layer 400. The protective
layer 400 can be applied by means of roll coating, gravure coating,
knife coating, dip coating, curtain flow coating, spray coating,
bar coating, die coating, spin coating or inkjet coating, by using
a dispenser, or other means.
[0072] FIG. 5 shows a method according to aspects of the present
disclosure. The method may comprise disposing a quantum dot
solution on a barrier layer, at step 502. The quantum dot solution
may be disposed on the barrier layer using a solution coating
process.
[0073] At step 504, the quantum dot solution may be cured to form a
quantum dot layer adhered to the barrier layer. The barrier layer
may comprise a polysilazane-based polymer, a polysiloxane-based
polymer, or a combination thereof.
[0074] At step 505, a protective solution is formed by mixing a
barrier polymer with a scavenger as discussed above. At step 506,
protective solution is disposed on the quantum dot layer. The
protective solution may be disposed on the quantum dot layer using
one or more of roll coating, gravure coating, knife coating, dip
coating, curtain flow coating, spray coating, bar coating, die
coating, spin coating or inkjet coating, by using a dispenser, or a
combination thereof.
[0075] At step 508, the protective solution may be cured to form a
protective layer adhered to the quantum dot layer. The protective
solution may be cured using one or more of a radiation curing
process including but not limited to a ultraviolet (UV) curing
process, and a thermal curing process including but not limited to
a steam curing process. The protective layer inhibits the
permeation of at least oxygen and moisture into the quantum dot
layer. The protective layer may optionally include a functional
layer disposed adjacent an inorganic layer. The inorganic layer of
the protective layer may include a polysilazane-based polymer, a
polysiloxane-based polymer, or a combination thereof. As a further
option, the protective layer may comprise, consists essentially of,
or consist of a functional layer disposed adjacent a hybrid layer.
The hybrid layer of the protective layer may comprises an organic
component and an inorganic component. The inorganic component may
comprise at least polysilazane-based polymer, a polysiloxane-based
polymer, or a combination thereof.
[0076] With reference to FIG. 6, a method 600 may comprise
disposing a quantum dot layer between a first layer and a second
layer at 602, mixing a barrier polymer and a scavenger at 604 to
form at least one of the first layer and the second layer. The
example shown in FIG. 5 encompasses forming a second layer with a
protective solution including a barrier polymer and a scavenger. It
will be understood that the construction of a film 200 where the
first layer only is a protective layer may be formed according to
the same method with the film inverted. FIG. 7 depicts an example
where both the first layer (eg., 202, FIG. 2) and second layer
(e.g., 204, FIG. 2) are formed from a protective solution including
a barrier polymer and a scavenger as described above. In this
example, the method 700 comprises providing a substrate at 701,
mixing a barrier polymer and a scavenger to form a protective
solution at 702; applying the protective solution to a substrate at
704. If needed to form first layer, the protective solution and
substrate may be cured at step 706. A quantum dot solution is
applied at step 708. If needed, the quantum dot solution is cured
to form a quantum dot layer on top of first layer at 710. A second
layer including the protective solution applied on quantum dot
layer at step 712. The second layer is applied opposite first layer
to cause quantum dot layer to be disposed between the first and
second layers. At step 714, an optional functional layer may be
applied to second layer. As discussed above functional layer may be
selected to achieve desired surface characteristics or finishes,
and may include a diffuser.
[0077] Once cured, the protective layer(s) may have a thickness
that is less than the thickness of the barrier layer. As an
example, the barrier layer may have a thickness of 100 microns and
the protective layer may have a thickness of less than 100 microns.
In another example, the protective layer 400 may have a thickness
of less than 50 microns. Since the protective layer may have a
thickness that is less than the barrier layer, the overall
thickness of the stack of layers may be minimized compared to a
stack having two of the barrier layers.
[0078] In accordance with the disclosures, providing a protective
layer comprised of a barrier polymer with a scavenger provides
higher intensity levels for light emitted from the quantum dot
layer in the film 200 over time. In particular, intensity levels in
films including a protective layer comprised of a barrier polymer
and scavenger as described herein degrade at a rate lower than the
rate for conventional quantum dot layers. The following experiment
demonstrates a comparison of films having a protective layer
created with solutions according to the disclosure having a
scavenger to a solution without a scavenger (control). These
solutions were then compared to a conventional quantum dot
film.
[0079] Through simulation, films prepared according to the
disclosure were compared to a conventional quantum dot layer to
test a protective layer including a barrier polymer mixed with a
scavenger according to the examples above. Protective solutions
were prepared for comparison against the conventional quantum dot
layer and a protective layer consisting of a barrier polymer
without scavenger present. Table 1 presents the formulation for
five prepared solutions. A first solution (Solution 1) included a
barrier polymer (polysilazane-based polymer) in solvent (butyl
ether) was created with 10% barrier polymer in 90% solvent and
applied to a quantum dot layer. Additional solutions added a
scavenger, where the amount of solvent was reduced in proportion to
the addition of the scavenger. Solution 2 included 0.01% scavenger.
Solution 3 included 0.1% scavenger. Solution 4 included 0.3%
scavenger. Solution 5 included 0.5% scavenger.
TABLE-US-00001 TABLE 1 Components of prepared solutions. Scaven-
Protocate- -- 0.01% 0.1% 0.3% 0.5% ger chuic acid Barrier
Polysilazane- 10% .sup. 10% 10% 10% 10% polymer based polymer
Solvent Butyl ether 90% 89.99% 89.9% 89.7% 89.5% Total 100% 100%
100% 100% 100%
[0080] In the experiment, protocatechuic acid (3,4-dihydroxybenzoic
acid) was used as the scavenger. FIG. 8 compares the measured
intensity of the quantum dot layer in a conventional quantum dot
film with solution 1 with the barrier polymer and solvent, and a
solution having barrier polymer and scavenger according to the
disclosure. It was observed that the conventional QD film intensity
level decreased more rapidly than the solution 1 and the protective
layer solution including a scavenger. FIG. 8 shows a slower rate of
decreasing intensity for both solutions compared to the
conventional film. The presence of the scavenger demonstrated a
much lower rate of decrease at the outset maintaining a relatively
high level of intensity in comparison to the sharp drop off in
intensity exhibited by the conventional QD film and the
non-scavenger control solution. Both of these solutions dropped
from an initial intensity of 1 (l/lo) to 0.8 or less in the first
50 hours. For the control solution, film stabilized after the
initial drop off exhibiting a decreasing intensity rate similar to
the rate demonstrated by the barrier polymer with the scavenger
present. The conventional QD film, however, continued to decrease
at a high rate until the intensity reached zero at about 300 hours.
Improved intensity stability was observed in the protective layer
solution including the scavenger. As noted, the initial rate of
decrease in intensity was markedly lower. The observed rate was
approximately 0.00004 PL per hour in the first 50 hours compared to
a rate of intensity loss in the control solution of about 0.004 PL
and similar rate of intensity loss in the conventional QD film.
Following the initial 50 hour period, the rate of decrease in
intensity for the barrier polymer with scavenger fell within a
range of about 0.00004 PL per hour and 0.0007 per hour.
Aspects
[0081] The present disclosure comprises at least the following
aspects.
[0082] Aspect 1A. An article comprising a first layer and a second
layer; a quantum dot layer disposed between the first layer and the
second layer; and wherein at least one of the first layer and the
second layer is a protective layer, the protective layer comprising
a barrier polymer and a scavenger, wherein the protective layer
inhibits the permeation of at least oxygen and moisture into the
quantum dot layer.
[0083] Aspect 1B. An article consisting essentially of: a first
layer and a second layer; a quantum dot layer disposed between the
first layer and the second layer; and wherein at least one of the
first layer and the second layer is a protective layer, the
protective layer comprising a barrier polymer and a scavenger,
wherein the protective layer inhibits the permeation of at least
oxygen and moisture into the quantum dot layer.
[0084] Aspect 1C. An article consisting of: a first layer and a
second layer; a quantum dot layer disposed between the first layer
and the second layer; and wherein at least one of the first layer
and the second layer is a protective layer, the protective layer
comprising a barrier polymer and a scavenger, wherein the
protective layer inhibits the permeation of at least oxygen and
moisture into the quantum dot layer.
[0085] Aspect 2. The film of example 1, wherein the scavenger is a
phenolic acid.
[0086] Aspect 3. The film of any one examples 1-2, wherein the
scavenger is a protocatechuic acid.
[0087] Aspect 4. The film of any one examples 1-3, wherein the
first layer is a barrier layer and wherein the quantum dot layer is
disposed on the barrier layer using a solution coating process.
[0088] Aspect 5. The film of examples 1-3, wherein the first layer
is a protective layer and the second layer is a protective layer,
wherein the first layer a substrate underlying the barrier polymer
and the scavenger.
[0089] Aspect 6. The film of any one of examples 1-5, wherein the
protective layer comprises the inorganic layer and the inorganic
layer comprises a polysilazane-based polymer, a polysiloxane-based
polymer, or a combination thereof.
[0090] Aspect 7. The film of any one of examples 1-6, wherein the
protective layer comprises the hybrid layer and the hybrid layer
comprises an organic component and inorganic component.
[0091] Aspect 8. The film of any one of examples 1-7, further
comprising a functional layer provided outward of the protective
layer.
[0092] Aspect 9. The film of any one of examples 1-8, wherein the
functional layer is a diffuser.
[0093] Aspect 10. The film of example 9, wherein the functional
layer is a prism.
[0094] Aspect 11. The film of any one of examples 1-9, wherein the
second layer is disposed on the quantum dot layer using a solution
coating process.
[0095] Aspect 12. The film of any one of claims 1-11, wherein the
scavenger is present in an amount less than 0.5%.
[0096] Aspect 13. The film of any one of claims 1-12, wherein the
scavenger is present in a range of about 0.01% to about 0.5%.
[0097] Aspect 14. The film of any one of claims 1-13, wherein the
protecting layer has a thickness in the range of about 50
nanometers to about 50 micrometers.
[0098] Aspect 15. A light emitting device comprising the film of
any one of examples 1-14.
[0099] Aspect 16A. A film for light emitting devices, the film
formed from a process comprising disposing a quantum dot solution
between a first layer and a second layer to form a quantum dot
layer, where at least one of the first layer and second layer is a
protective layer; and wherein the protective layer is formed by
mixing a barrier polymer with a scavenger.
[0100] Aspect 16B. A film for light emitting devices, the film
formed from a process consisting essentially of disposing a quantum
dot solution between a first layer and a second layer to form a
quantum dot layer, where at least one of the first layer and second
layer is a protective layer; and wherein the protective layer is
formed by mixing a barrier polymer with a scavenger.
[0101] Aspect 16C. A film for light emitting devices, the film
formed from a process consisting of: disposing a quantum dot
solution between a first layer and a second layer to form a quantum
dot layer, where at least one of the first layer and second layer
is a protective layer; and wherein the protective layer is formed
by mixing a barrier polymer with a scavenger.
[0102] Aspect 17. The film of example 16A, further comprising a
functional layer disposed adjacent to the second layer.
[0103] Aspect 18. The film of example 16A, wherein the barrier
polymer comprises a polysilazane-based polymer, a
polysiloxane-based polymer, or a combination thereof.
[0104] Aspect 19. The film of example 16A, wherein the protective
layer further comprises a functional layer.
[0105] Aspect 20. The film of example 19, wherein the functional
layer is a diffuser.
[0106] Aspect 21. The film of claim 19, wherein the functional
layer is a prism.
[0107] Aspect 22. The film of any one examples 16A-21, wherein the
first layer is a barrier layer.
[0108] Aspect 23. The film of any one examples 16A-22, wherein the
quantum dot solution is disposed on the barrier layer using a
solution coating process.
[0109] Aspect 24. The film of any one examples 16A-23, wherein the
protective layer is the second layer, and wherein the second layer
is disposed on the quantum dot layer using a solution coating
process.
[0110] Aspect 25. The film of any one examples 16A-24, wherein at
least one of the layers is cured using one or more of a radiation
curing process and a thermal curing process.
[0111] Aspect 26. The film of any one examples 24-25, wherein the
solution coating process includes at least one of roll coating,
gravure coating, knife coating, dip coating, curtain flow coating,
spray coating, bar coating, die coating, spin coating or inkjet
coating, by using a dispenser, or a combination thereof.
[0112] Aspect 27. A light emitting device comprising the film of
any one of examples 16-26.
[0113] Aspect 28A. A method comprising: disposing a quantum dot
solution on a first layer to form a quantum dot layer; applying a
second layer to the quantum dot solution; wherein at least one of
the first layer and second layer are a protective layer formed by
providing a barrier polymer with a scavenger, wherein the scavenger
absorbs at least one of oxygen and water to inhibit the at least
one of oxygen and water from reacting with the quantum dot
solution; and curing the first layer, second layer and quantum dot
solution to form a film comprising a stack of the first layer, the
quantum dot layer, and the second layer.
[0114] Aspect 28B. A method consisting essentially of: disposing a
quantum dot solution on a first layer to form a quantum dot layer;
applying a second layer to the quantum dot solution; wherein at
least one of the first layer and second layer are a protective
layer formed by providing a barrier polymer with a scavenger,
wherein the scavenger absorbs at least one of oxygen and water to
inhibit the at least one of oxygen and water from reacting with the
quantum dot solution; and curing the first layer, second layer and
quantum dot solution to form a film comprising a stack of the first
layer, the quantum dot layer, and the second layer.
[0115] Aspect 28C. A method consisting of: disposing a quantum dot
solution on a first layer to form a quantum dot layer; applying a
second layer to the quantum dot solution; wherein at least one of
the first layer and second layer are a protective layer formed by
providing a barrier polymer with a scavenger, wherein the scavenger
absorbs at least one of oxygen and water to inhibit the at least
one of oxygen and water from reacting with the quantum dot
solution; and curing the first layer, second layer and quantum dot
solution to form a film comprising a stack of the first layer, the
quantum dot layer, and the second layer.
Definitions
[0116] It is to be understood that the terminology used herein is
for the purpose of describing particular aspects only and is not
intended to be limiting. As used in the specification and in the
claims, the term "comprising" can include the aspects "consisting
of" and "consisting essentially of." Unless defined otherwise, all
technical and scientific terms used herein have the same meaning as
commonly understood by one of ordinary skill in the art to which
this disclosure belongs. In this specification and in the claims
which follow, reference will be made to a number of terms which
shall be defined herein.
[0117] Ranges can be expressed herein as from one value (first
value) to another value (second value). When such a range is
expressed, the range includes in some aspects one or both of the
first value and the second value. Throughout this document, values
expressed in a range format thus may be interpreted in a flexible
manner to include not only the numerical values explicitly recited
as the limits of the range, but also to include all the individual
numerical values or sub-ranges encompassed within that range as if
each numerical value and sub-range is explicitly recited. As used
herein, the terms "about" and "at or about" mean that the amount or
value in question can be the designated value, approximately the
designated value, or about the same as the designated value. For
example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%"
should be interpreted to include not just about 0.1% to about 5%,
but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the
sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within
the indicated range. The statement "about X to Y" has the same
meaning as "about X to about Y," unless indicated otherwise.
Likewise, the statement "about X, Y, or about Z" has the same
meaning as "about X, about Y, or about Z," unless indicated
otherwise. The term "about" as used herein can allow for a degree
of variability in a value or range, for example, within 10%, within
5%, or within 1% of a stated value or of a stated limit of a range,
and includes the exact stated value or range. The term
"substantially" as used herein refers to a majority of, or mostly,
as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%,
99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or
100%.
[0118] In this document, the terms "a," "an," or "the" are used to
include one or more than one unless the context clearly dictates
otherwise. The term "or" is used to refer to a nonexclusive "or"
unless otherwise indicated. The statement "at least one of A and B"
has the same meaning as "A, B, or A and B." In addition, it is to
be understood that the phraseology or terminology employed herein,
and not otherwise defined, is for the purpose of description only
and not of limitation. Any use of section headings is intended to
aid reading of the document and is not to be interpreted as
limiting; information that is relevant to a section heading may
occur within or outside of that particular section.
[0119] In the methods described herein, the acts can be carried out
in any order without departing from the principles of the
invention, except when a temporal or operational sequence is
explicitly recited. Furthermore, specified acts can be carried out
concurrently unless explicit claim language recites that they be
carried out separately. For example, a claimed act of doing X and a
claimed act of doing Y can be conducted simultaneously within a
single operation, and the resulting process will fall within the
literal scope of the claimed process.
[0120] The term "organic group" as used herein refers to any
carbon-containing functional group. For example, an
oxygen-containing group such as an alkoxy group, aryloxy group,
aralkyloxy group, oxo(carbonyl) group, a carboxyl group including a
carboxylic acid, carboxylate, and a carboxylate ester; a
sulfur-containing group such as an alkyl and aryl sulfide group;
and other heteroatom-containing groups. Non-limiting examples of
organic groups include OR, OOR, OC(O)N(R).sub.2, CN, CF.sub.3,
OCF.sub.3, R, C(O), methylenedioxy, ethylenedioxy, N(R).sub.2, SR,
SOR, SO.sub.2R, SO.sub.2N(R).sub.2, SO.sub.3R, C(O)R, C(O)C(O)R,
C(O)CH.sub.2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R).sub.2,
OC(O)N(R).sub.2, C(S)N(R).sub.2, (CH.sub.2).sub.0-2N(R)C(O)R,
(CH.sub.2).sub.0-2N(R)N(R).sub.2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR,
N(R)N(R)CON(R).sub.2, N(R)SO.sub.2R, N(R)SO.sub.2N(R).sub.2,
N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R).sub.2,
N(R)C(S)N(R).sub.2, N(COR)COR, N(OR)R, C(.dbd.NH)N(R).sub.2,
C(O)N(OR)R, C(.dbd.NOR)R, and substituted or unsubstituted
(C.sub.1-C.sub.100)hydrocarbyl, wherein R can be hydrogen (in
examples that include other carbon atoms) or a carbon-based moiety,
and wherein the carbon-based moiety can be substituted or
unsubstituted.
[0121] The term "substituted" as used herein in conjunction with a
molecule or an organic group as defined herein refers to the state
in which one or more hydrogen atoms contained therein are replaced
by one or more non-hydrogen atoms. The term "functional group" or
"substituent" as used herein refers to a group that can be or is
substituted onto a molecule or onto an organic group. Examples of
substituents or functional groups include, but are not limited to,
a halogen (e.g., fluorine F, chlorine C.sub.1, bromine Br, and
iodine I); an oxygen atom in groups such as hydroxy groups, alkoxy
groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups,
carboxyl groups including carboxylic acids, carboxylates, and
carboxylate esters; a sulfur atom in groups such as thiol groups,
alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups,
sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups
such as amines, hydroxyamines, nitriles, nitro groups, N-oxides,
hydrazides, azides, and enamines; and other heteroatoms in various
other groups. Non-limiting examples of substituents that can be
bonded to a substituted carbon (or other) atom include F, Cl, Br,
I, OR, OC(O)N(R).sub.2, CN, NO, NO.sub.2, ONO.sub.2, azido,
CF.sub.3, OCF.sub.3, R, O (oxo), S (thiono), C(O), S(O),
methylenedioxy, ethylenedioxy, N(R).sub.2, SR, SOR, SO.sub.2R,
SO.sub.2N(R).sub.2, SO.sub.3R, C(O)R, C(O)C(O)R, C(O)CH.sub.2C(O)R,
C(S)R, C(O)OR, OC(O)R, C(O)N(R).sub.2, OC(O)N(R).sub.2,
C(S)N(R).sub.2, (CH.sub.2).sub.0-2N(R)C(O)R,
(CH.sub.2).sub.0-2N(R)N(R).sub.2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR,
N(R)N(R)CON(R).sub.2, N(R)SO.sub.2R, N(R)SO.sub.2N(R).sub.2,
N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R).sub.2,
N(R)C(S)N(R).sub.2, N(COR)COR, N(OR)R, C(.dbd.NH)N(R).sub.2,
C(O)N(OR)R, and C(.dbd.NOR)R, wherein R can be hydrogen or a
carbon-based moiety; for example, R can be hydrogen,
(C.sub.1-C.sub.100)hydrocarbyl, alkyl, acyl, cycloalkyl, aryl,
aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or wherein
two R groups bonded to a nitrogen atom or to adjacent nitrogen
atoms can together with the nitrogen atom or atoms form a
heterocyclyl.
[0122] The term "alkyl" as used herein refers to straight chain and
branched alkyl groups and cycloalkyl groups. Examples of straight
chain alkyl groups include those with from 1 to 8 carbon atoms such
as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl,
and n-octyl groups. Examples of branched alkyl groups include, but
are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl,
neopentyl, isopentyl, and 2,2-dimethylpropyl groups.
[0123] The term "alkenyl" as used herein refers to straight and
branched chain and cyclic alkyl groups as defined herein, except
that at least one double bond exists between two carbon atoms.
[0124] The term "acyl" as used herein refers to a group containing
a carbonyl moiety wherein the group is bonded via the carbonyl
carbon atom.
[0125] The term "cycloalkyl" as used herein refers to cyclic alkyl
groups such as, but not limited to, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In
some aspects, the cycloalkyl group can have 3 to about 8-12 ring
members, whereas in other aspects the number of ring carbon atoms
range from 3 to 4, 5, 6, or 7
[0126] The term "aryl" as used herein refers to cyclic aromatic
hydrocarbon groups that do not contain heteroatoms in the ring.
Thus aryl groups include, but are not limited to, phenyl, azulenyl,
heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl,
triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl,
anthracenyl, and naphthyl groups.
[0127] The term "heterocyclyl" as used herein refers to aromatic
and non-aromatic ring compounds containing three or more ring
members, of which one or more is a heteroatom such as, but not
limited to, nitrogen N, oxygen O, and sulfur S.
[0128] The term "alkoxy" as used herein refers to an oxygen atom
connected to an alkyl group, including a cycloalkyl group, as are
defined herein.
[0129] The terms "halo," "halogen," or "halide" group, as used
herein, by themselves or as part of another substituent, mean,
unless otherwise stated, a fluorine, chlorine, bromine, or iodine
atom.
[0130] The term "haloalkyl" group, as used herein, includes
mono-halo alkyl groups, poly-halo alkyl groups wherein all halo
atoms can be the same or different, and per-halo alkyl groups,
wherein all hydrogen atoms are replaced by halogen atoms, such as
fluoro. Examples of haloalkyl include trifluoromethyl,
1,1-dichloroethyl, 1,2-dichloroethyl,
1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.
[0131] The term "hydrocarbon" or "hydrocarbyl" as used herein
refers to a molecule or functional group, respectively, that
includes carbon and hydrogen atoms. The term can also refer to a
molecule or functional group that normally includes both carbon and
hydrogen atoms but wherein all the hydrogen atoms are substituted
with other functional groups.
[0132] As used herein, the term "hydrocarbyl" refers to a
functional group derived from a straight chain, branched, or cyclic
hydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl,
acyl, or any combination thereof. Hydrocarbyl groups can be shown
as (C.sub.a-C.sub.b)hydrocarbyl, wherein a and b are integers and
mean having any of a to b number of carbon atoms. For example,
(C.sub.1-C.sub.4)hydrocarbyl means the hydrocarbyl group can be
methyl (C.sub.1), ethyl (C.sub.2), propyl (C.sub.3), or butyl
(C.sub.4), and (C.sub.0-C.sub.b)hydrocarbyl means in certain
aspects there is no hydrocarbyl group.
[0133] The term "number-average molecular weight" (M.sub.n) as used
herein refers to the ordinary arithmetic mean of the molecular
weight of individual molecules in a sample. It is defined as the
total weight of all molecules in a sample divided by the total
number of molecules in the sample. Experimentally, M.sub.n is
determined by analyzing a sample divided into molecular weight
fractions of species i having n.sub.i molecules of molecular weight
M.sub.i through the formula
M.sub.n=.SIGMA.M.sub.in.sub.i/.SIGMA.n.sub.i. The M.sub.n can be
measured by a variety of well-known methods including gel
permeation chromatography, spectroscopic end group analysis, and
osmometry. If unspecified, molecular weights of polymers given
herein are number-average molecular weights.
[0134] The term "weight-average molecular weight" as used herein
refers to M.sub.w, which is equal to
.SIGMA.M.sub.i.sup.2n.sub.i/.SIGMA.M.sub.in.sub.i, where n.sub.i is
the number of molecules of molecular weight M.sub.i. In various
examples, the weight-average molecular weight can be determined
using light scattering, small angle neutron scattering, X-ray
scattering, and sedimentation velocity.
[0135] The term "radiation" as used herein refers to energetic
particles travelling through a medium or space. Examples of
radiation are visible light, infrared light, microwaves, radio
waves, very low frequency waves, extremely low frequency waves,
thermal radiation (heat), and black-body radiation.
[0136] The term "UV light" as used herein refers to ultraviolet
light, which is electromagnetic radiation with a wavelength of
about 10 nm to about 400 nm.
[0137] The term "cure" as used herein refers to exposing to
radiation in any form, heating, or allowing to undergo a physical
or chemical reaction that results in hardening or an increase in
viscosity.
[0138] The term "solvent" as used herein refers to a liquid that
can dissolve a solid, liquid, or gas. Non-limiting examples of
solvents are silicones, organic compounds, water, alcohols, ionic
liquids, and supercritical fluids.
[0139] The term "coating" as used herein refers to a continuous or
discontinuous layer of material on the coated surface, wherein the
layer of material can penetrate the surface and can fill areas such
as pores, wherein the layer of material can have any
three-dimensional shape, including a flat or curved plane. In one
example, a coating can be formed on one or more surfaces, any of
which may be porous or nonporous, by immersion in a bath of coating
material.
[0140] The term "surface" as used herein refers to a boundary or
side of an object, wherein the boundary or side can have any
perimeter shape and can have any three-dimensional shape, including
flat, curved, or angular, wherein the boundary or side can be
continuous or discontinuous. While the term surface generally
refers to the outermost boundary of an object with no implied
depth, when the term `pores` is used in reference to a surface, it
refers to both the surface opening and the depth to which the pores
extend beneath the surface into the substrate.
[0141] As used herein, the term "polymer" refers to a molecule
having at least one repeating unit and can include copolymers.
[0142] The polymers described herein can terminate in any suitable
way. In some aspects, the polymers can terminate with an end group
that is independently chosen from a suitable polymerization
initiator, --H, --OH, a substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl (e.g., (C.sub.1-C.sub.10)alkyl or
(C.sub.6-C.sub.20)aryl) interrupted with 0, 1, 2, or 3 groups
independently selected from --O--, substituted or unsubstituted
--NH--, and --S--, a poly(substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyloxy), and a poly(substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbylamino).
[0143] Illustrative types of polyethylene include, for example,
ultra-high molecular weight polyethylene (UHMWPE, for example, a
molar mass between 3.5 and 7.5 million atomic mass units),
ultra-low molecular weight polyethylene (ULMWPE), high molecular
weight polyethylene (HMWPE), high density polyethylene (HDPE, for
example, a density of about 0.93 to 0.97 grams per cubic centimeter
(g/cm.sup.3) or 970 kilograms per cubic meter (kg/m.sup.3)), high
density cross-linked polyethylene (HDXLPE, for example, a density
of about 0.938 to about 0.946 g/cm.sup.3), cross-linked
polyethylene (PEX or XLPE, for example, a degree of cross-linking
of between 65 and 89% according to ASTM F876), medium density
polyethylene (MDPE, for example, a density of 0.926 to 0.940
g/cm.sup.3), low density polyethylene (LDPE, for example, about
0.910 g/cm.sup.3 to 0.940 g/cm.sup.3), linear low density
polyethylene (LLDPE) and very low density polyethylene (VLDPE, for
example, a density of about 0.880 to 0.915 g/cm.sup.3).
[0144] It will be apparent to those skilled in the art that various
modifications and variations can be made in the present disclosure
without departing from the scope or spirit of the disclosure. Other
aspects of the disclosure will be apparent to those skilled in the
art from consideration of the specification and practice of the
disclosure disclosed herein. It is intended that the specification
and examples be considered as exemplary only, with a true scope and
spirit of the disclosure being indicated by the following
claims.
[0145] The patentable scope of the disclosure is defined by the
claims, and can include other examples that occur to those skilled
in the art. Such other examples are intended to be within the scope
of the claims if they have structural elements that do not differ
from the literal language of the claims, or if they include
equivalent structural elements with insubstantial differences from
the literal languages of the claims.
* * * * *